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July 29, 1952 K. M. GAVER ET AL 23,528

- REACTION OF GLUCOPYRANOSE POLYMERS WITH SUBSTITUTED AMMONIUM HYDROXIDES Original Filed Aug. 1, 1947 Malaria], con liaining a Jubflfitutel ammonium hgdroxgl group on u. hydroxide Base oarbon rfllom acljmccn t To a. (c gftciramuzyl carbonyl grou k ufliorch) ammonium hgmlroxile) tm mm-re of about 61's OI (LLOUC.

suhi'vfilutul Product Removal ofwofber. Containing the nitrogen radical Fig.1

, v INVENTOR.

a KENNETH M. GA! ER. I ESTHER. P. LEISURE LE VI M. THOMAS EMW THEIR. ATIOR-NEY Reissued July 29, 1952 WITH DROXIDE S SUBSTITUTED AMMONIUM HY- Kenneth M. Gaver and Esther P. Lasure, Grove City, and Levi M. Thomas, Columbus, Ohio. assignors to The Keever Starch Company, Golumbus, Ohio, a corporation of Ohio Original No. 2,563,526, dated August 7, 1951, Se-

' rial No. 765,370, August 1, 1947. Application for reissue March 22, 1952, Serial No. 277,936 a 12 Claims.

1 This-application-is an application for reissue of Patent No. 2,563,526, granted on August 7, 1951.

The inventions disclosed in this application relate to new compositions of matter and to new processes for the formation of such new compo- 'sitions'of;matter. The new compositions of matter invented by us result from the chemical reactions of primary, secondary, tertiary or quaternary substituted ammonium hydroxides with carbohydrates and similar material. Examples of the substituted ammonium hydroxides are:

and"

(where each R may be any monovalent organic radical). The carbohydrate may be any aldehyde or ketone derivative of a polyhydric alcowhere .1: equals the number of carbon atoms per unit and n equals the number of units per molecule. Materials similar to carbohydrates which may be reacted similarly with the substituted ammonium hydroxides are carbohydrate containing materials and similar materials containing a'hydro-xyl group on a carbon atom adjacent to a carbonyl or potentially carbonyl group. When such substituted ammonium hydroxides are reacted with the carbohydrate or similar material under proper conditions later to be described herein, the hydroxyl of the hydroxide forms water with hydrogen of the most acidic of the carbohydrate (or similar material) hydroxyls and the remainder of substituted ammonium hydroxide is substituted so as to form a carbohydrate having a formula of where each G is either a hydrogen atom or any monovalent organic radical and where R may be any monovalent organic radical. The processes described herein illustrating our inventions are especially designed to produce such new products from carbohydrates.

The new compositions of matter produced from the reactions of quaternary bases with starches are good examples thereof. In the production of such new compositions of matter from the reactionof quaternary bases with starch, the new process comprises ordinarily a step of reacting starch with a quaternary base so as to produce a compound composed of an undeterminednumber of polymerized glucopyranose units all or most of which units will each have a general structural formula substantially as follows:

where R, R, R" and R' may be the same or different monovalent organicradicals. To designate compounds conforming to the above formula Weuse the terms quaternary starchates which we define as follows: Quaternary starchate means and is used in this specification and in the claims hereof in the sense of the compound composed of an undetermined. number of polymerized glucopyranose units wherein a quinquevalent nitrogen having. four substituent organic radicals attached thereto issubstituted for one of the hydrogen atoms of one of the several hydroxyl groups of the starch unit so as to form a polymerized compound which in fact is (or is at least analogous to) an alcoholate or ether of starch.

As used in this specification and claims we define carbohydrate to mean any aldehyde or ketonederivative of a polyhydric alcohol" and starchate to mean "any compound composed of an undetermined number of polymerized-glucopyranose units wherein onev or more ,metallic or nonmetallic atoms or organic or inorganic radicals are substituted for one or more of the hydrogen atoms of the several hydroxyl groups of the starch unit to form a polymerized compound whichin factv is (or at least is analogous to) an alcoholate or ether of starc Y Prior to our inventions as disclosed herein a certain process has been discovered for. the substitution of alkaline metals in thestarch molecule which we will refer to hereinafter as the ammonia process starchate. As demonstrated in copending application Serial No. 694,328 of Kenneth M. Gaver, Esther P. Lasure and 'Derk V. Tieszen and in ,Patent No. 2,518,135 issued 'to Kenneth M. Gaver on August 8; 1950, and as demonstrated hereafter in this application such prior 'artproces'ses produce starchates which differ essentially from the starchates disclosedin this application as being formed by our improved 3 process. In copending application Serial No. 747,108, we have disclosed certain amidogen starchates and processes for their synthesis. Also in said copending application Serial No. 694,328 and in said Patent 2,518,135 there is disclosed the formation of a monosodium starchate, other monoalkali starchates and monometallic, monononmetallic and monoorganic derivatives thereof but as was demonstrated in said copending applications and as will be demonstrated hereafter herein, such starchates also differ from vision of tetra-substituted ammonium hydroxide .starchates and of new methods of synthesizing such compounds.

QA- further object of our invention is the provision of new and useful processesfor forming various new products'from starch.

"Further objects and advantages of the present invention will be apparent from the following description, reference being had tothe accompanying-drawings wherein a preferred form of embodiment of the invention is clearly shown.

In the drawings: I #Figpl illustrates methods of synthesizing the desired products.

In said copending applications Serial No. 594,328 and No." 707, 318, nowP-atentNoi 2,518,135, there are disclosed inventions relating to monometallic starchates 3 (both alkali and 'nonalkali) -to' monononmetallic starchates, to -monoor'ganic :starchates, and to hydrolysis products of-such -starchates and to methods fortheirpreparation.

I We have discovered that where a carbohydrate '-(orsimilarmaterial) is reacted in a nonaqueous system with .a primary, secondary, tertiary or *quaternaryammonium hydroxide as illustrated :above, at a temperature of from 80-81 C., a reaction occurs in which water-is evolved and :thecarbohydrate -(or similar material) is con- Ldensed-with the substituted ammonium hydroxide to form asubstituted ammonium carbohydrate product. Specifically, for example, where -starchis reacted in a nonaqueous solvent with .Lquaternary base; at a temperature of from -:80-'8:1 C., asreaction occurs and water'is evolved (comprising the hydrogen of the number two .hydroxyl 'from' the glucopyranose unit of the -starch'and the hydroxyl of the quaternary base) ito: form the substituted ammonium starchate.

OF CARBOHYDRATE 'USABLE' 'Any type of ,carbohydrateis usable as is any other compound havinga hydroxyl' group on the 'dextran; sugars such as sucrose; glucosides such as a-methyl glucoside; cellulose 'suchas cotton, "linen, jute and 'ramie; inulin; and gums'such "as locust bean gum,tragacanth and gumarabic.

4 SOLVENTS Any nonaqueous system is suitable. If a solvent is used it preferably should be substantially nonaqueous. Any of the higher boiling alcohols -may be used as solvents although we prefer toluene and consider butanol as very useful. Ketones, ethers and other hydrocarbon solvents may be used. In some cases no solvent need be used at all. For example, starch and a quaternary base will react dry.

TEMPERATURE A temperature of -81 C. appears to be critical. Using temperatures up to C. with :or without the removal of the water, we have found no evidence indicating the formation of any derivative other than mono.

PRESSURE We observed no particular benefits or :detriments derived from-pressure reaction.

TINLE I The time factor undoubtedly has considerable influence on the reaction. However, prolonged reaction periods donotseem to produce-better reactions than short vigorous reactions. N0 logical .study has been given to this variable.

REMOVAL OF WATER Preferablythe water formed by the reaction should be removed substantially as formed as also should most of any other waterpresent in the system (as for example water contained in the carbohydrate orin the solvent).

One of the most practical methods of removing water is by distillation. For example, water forms an azeotrope with many of the useful'solvents enabling us to distil the water originally present in the system and the water formed by the reaction with a portion of the solvent while retaining in the system the main body of the solvent inasmuch as the azeotrope boils below the boiling point of the solvent as well asbelow thefboilin'g point of water. Y

Theprocess of removing waterffromthereacting ssytems is disclosed and claimed-in our copending application Serial 'No. 24,628 filed May 1, 1948.

CHARACTER OF AMMONIUM HYDROXIDE Where a quaternary base is mixed with the carbohydrate at a temperature-of 80-81 0., little difiiculty is experienced with the reaction.

Where a tertiary base is used, greater difiiculty is experienced and the difficulty ininducing the reaction is increased. as the ionization constant is reduoed'when using the secondaryand primary bases. It was found that an ionizationiconstant of 2 ll) was very desirable in reactionsinvolv ing alkali hydroxides such as sodium'hydroxide with starch. However, with the uaternary bases an ionization constant as low as 10- Ji fs or unsubstituted ammonium I hydroxide tdweact.

PROPERTIES 0F THEPRODUCTS The products "formed hydrolyze immediately but not completely in water. They are'decom posed by acids. They are subject to replacement of the N(R4) group bymetals when reacted with metallic halides as is shown in the following Equation 1. They are subject to replacement of the N(R4) group by nonmetals when reacted with nonmetallic halides as is shown in the following Equation 2. The MR4) group also may be replaced by organic groups according to Equation 3 following:

(where a equals one or more; M equals any metal; D an inorganic nonmetal; R an organic group; and X is a halogen or similarly reacting group such as, for example, a nitrate, etc.).

MECHANISM OF THE REACTION The mechanism of the reaction proceeds along lines similar to those illustrated by the following equations:

(1) Addition CGHIOOB +R4NOH CsH1005 HONR4 (2) Dehydration CsI-ImOs HONR4 C6H905NR4+H2O EXAMPLES Example I 50 grams of corn starch 60 grams of benzyl trimethyl ammonium hydroxide 500 ml. of toluene Heat with agitation and slow distillation until 250 ml. of distillate have been collected. Filter on suction, wash with toluene and then with ether and then air dry. Water is evolved in this reaction. Air dry weight of product 82 grams (calculated 89 grams). This weight yield approximates that obtained in the sodium starchate reaction. Distillate is neutral.

Emumple II 200 grams wheat dextrin 91 grams anhydrous tetramethyl ammonium hydroxide 900 ml. normal butanol 200 grams locust bean gum 103 grams neur-ine (trimethylvinyl ammonium hydroxide)- 2000 ml. benzene This mixture was heated with vigorous agitation at boiling temperatures with distillation until 1000 ml. of distillate was collected. The moisture originally present and that liberated in the reaction was removed from the reaction mixture as the benzene azeotrope. At the end of the reaction period the reaction product is filtered on suction, washed with benzene then with ether and air dried. Air dry weight 282 grams. The product is a pale buff free-flowing powder.

It is to be understood that the above described embodiments of our invention are for the purpose of illustration only and various changes may 1. A process of forming uniformly substituted nitrogen containing glucopyranose polymers which comprises mixing glucopyranose polymers with a substituted ammonium hydroxide at a temperature in the range of C. to ..C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction;

2'. A process of forming uniformly substituted nitrogen containing glucopyranose polymers which comprises mixing glucopyranose polymers with a tetra substituted ammonium hydroxide in the range of from 80 C. to 115" C". in a substantially nonaqueous system. 3. A process of forming a uniformly-sub stituted nitrogen containing starchate which comprises the process of heating a mono substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

4. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a (ii-substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

5. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a tri-substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

6. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a tetra-substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially non-aqueous system with provision for substantial removal of water formed by the reaction.

'7. A new composition of matter consisting of uniformly substituted glucopyranose polymers substantially all units of which have a formula of where R. is a monovalent alkyl radical having not more than four carbon atoms, and where each R, R" and R' is a substituent selected from the group consisting of hydrogen and monovalent alkyl radicals having not more than four carbon atoms.

8. A new composition of matter formed by the reaction of glucopyranose polymers in a substantially nonaqueous system at a temperature of about 81 C. to about 115 C. with a substituted ammonium hydroxide and consisting of uniformly substituted glucopyranose polymers substantially all units of which have a structural formula of where R is a monovalent alkyl radical having not more than four carbon atoms and where each seams CIR 'and R iisia 'substitue'nt selected-.Irom

the group consisting of hydrognand rmonova lent alkyl radicals having .not more thanicur carbon atoms. 1

9. A starchate substantially each unitccf which has'theg'enerai structural formula of O HOCH;;(H(CH)(OHOH)(GHONRQCHO- where eachv R may be :;any moniovalent alkyl -radical having :notL-mor'e than four carbon atoms.

'10. A starchate substantially -:each unit- 0f which has the general structural formula of where R is-a .monovalent -a1kyl radical (haying vnot more than four carbon (atoms.

11. A starchate -substantially -each--unit-of which. has the. general: structural -fcrmula "of where each: R1 is ra monovalent alkyl radical having not :morethan four carbon atoms.

12. A starchate substantially each unit of which :has the general structural vformula 'of KENNETH.M. GAVER.. ESI'HER P. LASURE LEVI M. THOMAS.

REFERENCES CITED The-following references areof-record in the file of this patent crthe original patent:

UNITED STATES PATENTS Number Name Date 13986381 Dreyfus -Jan.' 8, 1935 2,009,015 *Powers'et al July-2-3, 1935 

